Preparation of urethane and carbonate products

Abstract

The present invention provides a process for preparing urethanes and carbonates from an amine or an alcohol, carbon dioxide and an allyl halide. The amine or alcohol is reacted with carbon dioxide to form the ammonium carbamate or carbonate salt which is then reacted with a palladium tertiary phosphine catalyst complex of an allyl halide. Polymer products can also be prepared utilizing this process or utilizing the resulting urethanes and carbonates under standard polymerization conditions.

What is claimed is: 
     
       1. A process for preparing urethanes and carbonates comprising: a) bringing CO 2  and a primary or secondary amine, an alcohol, an aminoalcohol, or a mixture thereof into reactive contact in the presence of a tertiary amine base, and in a solvent to form the corresponding ammonium carbamate salt or carbonate salt, and   b) reacting said salt with an allyl halide in the presence of a palladium tertiary phosphine catalyst system.   
     
     
       2. The process of claim 1 wherein said solvent is selected from the group consisting of THF, DMSO,1,2-dimethoxyethane, and glyme. 
     
     
       3. The process of claim 1 wherein the solvent is an etherated solvent. 
     
     
       4. The process of claim 1 wherein the solvent is selected from the group consisting of THF and glyme. 
     
     
       5. The process of claim 1 wherein the palladium tertiary phosphine catalyst system is selected from the group consisting of tris(dibenzylideneacetone)dipalladium+2-bis (diphenylphosphino)ethane, tetrakis (triphenylphosphine)palladium+tris(dibenzylideneacetone)dipalladium; and +triphenylphosphine+triphenylphosphine. 
     
     
       6. The process of claim 1 wherein said tertiary amine base is selected from the group consisting of amidines and guanidines. 
     
     
       7. The process of claim 1 wherein said tertiary amine base is selected from the group consisting of DBU, DBN, MTBD and CyTMG. 
     
     
       8. A process of preparing a compound of the formula: ##STR8## wherein R 1  represents an allyl radical; A represents a radical selected from the group consisting of --NR 2  R 3  and --OR 4  wherein R 2 , R 3  and R 4  independently represent hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl or aralkenyl radicals having from 1 to about 22 carbon atoms; or R 2  and R 3  together with the nitrogen of the radical --NR 2  R 3  may be bound to form a heterocyclic 5 to 9 membered ring radical; or R 2  or R 3  represents a radical of the formula ##STR9## or R 4  represents a radical of the formula ##STR10## wherein R represents hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl or aralkenyl radicals having from 1 to about 22 carbon atoms; R 5  represents an alkylene radical having from 1 to about 22 carbon atoms and n represents an integer of from 0 to about 8; comprising: a) bringing CO 2  and a primary or secondary amine, an alcohol, an aminoalcohol, or a mixture thereof into reactive contact in the presence of a tertiary amine base, and in a solvent to form the corresponding ammonium carbamate salt or carbonate salt, and   b) reacting said salt with an allyl halide in the presence of a palladium tertiary phosphine catalyst system.   
     
     
       9. The process of claim 8 wherein said compound is a urethane of the formula: ##STR11## wherein R 1  represents an allyl radical; R 2  and R 3  independently represent hydrogen and alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl and aralkenyl radicals having from 1 to about 22 carbon atoms; or wherein one of R 2  and R 3  represent a radical of the formula ##STR12## wherein R 1  is as defined above, R represents hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl or aralkenyl radicals having from 1 to about 22 carbon atoms, R 5  represents alkylene radicals having from 1 to about 22 carbon atoms and n represents an integer of from 0 to about 8; or wherein R 2  and R 3  together with the nitrogen are bound to form a saturated or unsaturated heterocyclic 5 to 9 membered ring radical. 
     
     
       10. The process of claim 8 wherein said compound is a carbonate of the formula ##STR13## wherein R 1  represents an allyl radical and R 4  represents alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl or aralkenyl radicals having from 1 to about 22 carbon atoms and radicals represented by the formula ##STR14## wherein R 1  represents radicals as defined above, R 5  represents alkylene radicals having from 1 to about 22 carbon atoms, and n represents an integer of from 0 to 8. 
     
     
       11. The process of claim 8 wherein said solvent is selected from the group consisting of THF, DMSO, 1,2-dimethoxyethane, and glyme. 
     
     
       12. The process of claim 8 wherein the solvent is an etherated solvent. 
     
     
       13. The process of claim 8 wherein the solvent is selected from the group consisting of THF and glyme. 
     
     
       14. The process of claim 8 wherein the palladium tertiary phosphine catalyst system is selected from the group consisting of tetrakis (triphenylphosphine)palladium+2-bis (diphenylphosphino)ethane, tetrakis (triphenylphosphine)palladium; tris(dibenzylideneacetone)dipalladium+triphenylphosphine; and triphenylphosphine. 
     
     
       15. The process of claim 8 wherein said tertiary amine base is selected from the group consisting of amidines and guanidines. 
     
     
       16. The process of claim 8 wherein said tertiary amine base is selected from the group consisting of DBU, DBN, MTBD and CyTMG. 
     
     
       17. The process of claim 8 wherein when R, R 2 , R 3  or R 4  is an aryl radical, said aryl radical is selected from the group consisting of alkenaryl and alkaryl radicals. 
     
     
       18. The process of claim 9 wherein when R, R 2  or R 3  is an aryl radical, said aryl radical is selected from the group consisting of alkenaryl and alkaryl radicals. 
     
     
       19. The process of claim 10 wherein when R 4  is an aryl radial, said aryl radial is selected from the group consisting of alkenaryl and alkaryl radicals.